Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
  • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/30—Only oxygen atoms
  • C07D251/34—Cyanuric or isocyanuric esters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0235—Nitrogen containing compounds
  • B01J31/0239—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate

Definitions

• the present invention relates to a process for the preparation of isocyanurates from diisocyanates.
• Isocyanurates are valuable starting materials for the production of polyurethane paints. In this respect, processes for their production are also of great interest.
• EP 0 082 987 A2 discloses a process for the preparation of isocyanurates from mixtures containing MPDI and EBDI. The preparation takes place within 1-60 minutes at temperatures of 40-140 ° C. in the presence of a catalyst, which can preferably be a quaternary ammonium salt of an organic acid.
• EP 1 170 283 A2 discloses a process for the production of low-odor and storage-stable isocyanurates, in which IPDI is reacted within 30 seconds to 2 hours at temperatures from 0 to 200 ° C. in the presence of a catalyst, which can be an ammonium salt of an acid.
• EP 1 273 603 A1 discloses a process for the production of low-odor and storage-stable isocyanurates, in which IPDI is reacted within 3 minutes to 3 hours at temperatures of 0-160 ° C. in the presence of a catalyst with at least one quaternary nitrogen atom based on a tricyclic diamine.
• EP 1 454 933 A1 discloses a process for the production of low-odor and storage-stable isocyanurates, in which IPDI within 2-30 minutes at temperatures of 20-120 ° C and in a pressure range of 0.5-5 bar in the presence of a catalyst with at least one quaternary nitrogen atom based on a tricyclic diamine is implemented and then the catalyst is thermally deactivated.
• the present invention relates to a process for the preparation of isocyanurate from diisocyanate.
• the starting material “diisocyanate” can be a single diisocyanate or a mixture of diisocyanates.
• the starting material is preferably exactly one diisocyanate.
• At least one of the diisocyanates used is preferably a (cyclo) aliphatic diisocyanate; H. a diisocyanate with at least one isocyanate group bonded directly to an aliphatic ring and optionally a further aliphatically bonded (i.e. to an isocyanate group connected to the aliphatic ring via an alkylene radical). It is further preferred to use only one (cyclo) aliphatic diisocyanate. Very particularly preferably at least one of the diisocyanates used is isophorone diisocyanate (IPDI) or 4,4'-diisocyanatodicyclohexylmethane (H12MDI). Isophorone diisocyanate is even more preferably used as the only diisocyanate. If isophorone diisocyanate is used, it is irrelevant whether it was obtained via the urea process or via the phosgene process.
• IPDI isophorone diisocyan
• isocyanurate is principally a product mixture containing isocyanurate groups, comprising chain-like and crosslinked polyisocyanatoisocyanurates, triisocyanatomonoisocyanurates (“trimers”) and, if appropriate, precursors of trimer formation.
• the product mixture containing isocyanurate groups is preferably a monomer-containing trimer which can be produced by a partial trimerization of diisocyanate.
• the process according to the invention for the preparation of isocyanurate is thus preferably a process for the partial trimerization of diisocyanate, in which essentially triisocyanatomonoisocyanurates and precursors of isocyanurates are formed.
• the peroxide content in the diisocyanate to be used is determined.
• the peroxide content is determined in accordance with DIN EN ISO 27 107 and is determined in mmol / kg.
• Before the reaction is preferably to be understood as meaning a time window of 14 days to 5 minutes before the starting material and catalyst are mixed. It is very particularly preferred to understand this to be a point in time of 2 days before the reaction.
• the peroxide content of the diisocyanate to be used is the peroxide content in mmol based on the total mass of the diisocyanate to be used in kilograms. If more than one diisocyanate is used to produce isocyanurate, the peroxide content of the diisocyanate to be used is the total peroxide content in mmol based on the total mass of all diisocyanates to be used in kilograms.
• the peroxide content determined as defined above is less than or equal to 10 mmol / kg, no further action is taken, since no significant disadvantages are to be expected from the presence of such a concentration of peroxide.
• the starting material (s) can thus be converted directly to isocyanurate.
• the diisocyanate educt is subjected to purification by distillation. If isocyanurate is to be produced from just one diisocyanate, each batch of the diisocyanate with a peroxide content greater than 10 mmol / kg is purified by distillation until the peroxide content of each batch is less than or equal to 10 mmol / kg.
• each batch of each diisocyanate whose peroxide content is greater than 10 mmol / kg is purified by distillation until the peroxide content of each batch of each diisocyanate is less than or equal to 10 mmol / kg.
• distillation Preference is given to purification by distillation in suitable distillation columns or distillation units, e.g. B. Short-path or thin-film distillation apparatus, carried out at suitable pressures and temperatures depending on the boiling point of the diisocyanates.
• the minimum distillation temperature should preferably not fall below 100.degree.
• the conversion of diisocyanate to isocyanurate is preferably carried out in the presence of at least one catalyst at temperatures of 0-160.degree.
• the pressure is not set separately and corresponds to the ambient pressure, which is close to 1 bar.
• Preferred reaction temperatures are 40-140.degree. C. and even more preferably 60-130.degree.
• Preferred reaction times are between 3 minutes and three hours.
• Suitable catalysts can be selected from the group consisting of tertiary amines, alkali metal salts of carboxylic acids, quaternary ammonium salts, aminosilanes and quaternary hydroxyalkylammonium salts.
• Preferred catalysts are N- (2-hydroxypropyl) -N, N, N-trimethylammonium-2-ethylhexanoate (75% strength in diethylene glycol available as DABCO TMR), or OH-containing quaternary ammonium compounds (available, for example, as EP BZ 7078 B from Evonik).
• the catalyst is preferably used in amounts of 0.05-1.5% by weight, more preferably in amounts of 0.1-0.8% by weight, even more preferably 0.4-0.7% by weight %, based on the mass of diisocyanate used.
• the reaction can optionally be carried out in the presence of at least one cocatalyst, at least one solvent and / or at least one auxiliary.
• Preferred co-catalysts can be selected from the group consisting of OH-functionalized compounds and Mannich bases from secondary amines and aldehydes or ketones.
• the catalyst is preferably dissolved with this in order to achieve more precise metering and optimal mixing.
• Solvents are preferably selected from water, low molecular weight alcohols (in particular methanol and ethylene glycol) and low molecular weight organic acids (in particular acetic acid or hexanoic acid).
• the process according to the invention can be carried out both batchwise and continuously. It is preferably carried out in a batch process.
• the process according to the invention is very particularly preferably carried out as a process for the partial trimerization of diisocyanate; H.
• the aim is to achieve a conversion well below 100% (determined by the residual NCO group content), preferably between 20 and 80%, more preferably between 25 and 60%, even more preferably between 30 and 45% .
• the conversion is simply carried out via a titrimetric NCO number determination based on DIN EN ISO 14896: 2009-07, i.e. H. a sample amount is dissolved in a non-protic solvent (e.g. acetone or ethyl acetate), then an excess of dibutylamine is added and the unreacted portion is back-titrated with 0.1% hydrochloric acid.
• a non-protic solvent e.g. acetone or ethyl acetate
• the disocyanate is allowed to react in the presence of the catalyst, optionally with the use of solvents and / or auxiliaries, until the desired conversion is achieved. If the reaction does not stop when the desired conversion is achieved, it can be stopped by deactivating the catalyst become. This can be done by adding a catalyst inhibitor such as p-toluenesulfonic acid, hydrogen chloride or dibutyl phosphate.
• a catalyst inhibitor such as p-toluenesulfonic acid, hydrogen chloride or dibutyl phosphate.
• isophorone diisocyanate 100 g are heated to 100 ° C. and mixed with 0.5% of a trimerization catalyst (DABCO TMR, Air Products or Vestanat EP BZ 7078 B, Evonik). The mixture is heated by an exothermic reaction to a temperature below 160 ° C. and is then cooled. The residual NCO content and thus the conversion and the color number are determined.
• DABCO TMR Trimerization catalyst

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Polyurethanes Or Polyureas (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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Citations (5)

• 2020
  • 2020-01-06 EP EP20150329.9A patent/EP3845576A1/fr not_active Withdrawn
  • 2020-12-18 US US17/126,152 patent/US20210206730A1/en not_active Abandoned
• 2021
  • 2021-01-05 CN CN202110006544.9A patent/CN113072513A/zh active Pending
  • 2021-01-05 JP JP2021000495A patent/JP2021109973A/ja active Pending

Patent Citations (5)

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